Method of hydrogenating an unsaturated fatty oil coated base and product thereof



Patented May 29, 1951 METHOD OF HYDROGENATING AN UN SATU- RATED PRODUCT THEREOF Mortimer T. Harvey, South Orange, N. J., assignor to HarvelResearch Corporation, a corporation of New Jersey FATTY OIL COATED. BASE AND No Drawing. Application June 11, 1948, Serial No. 32,523

Claims. 1

V This invention relates to novel products and to methods for making them. In oneof its more specific aspects the invention is directed to, novel and improved electrical insulatingpmaterial such as cable cloth, insulator wrapping, separators, etc. and to methods for producing it.

Cable cloth generally comprises a thermoset composition produced by heat converting a composition comprising a heat polymerizable unsaturated fatty oil, one or more oil-soluble resins and a metallic drier combination coated onto a flexible base. Such cable cloth has found extensive use as a wrapper for electric conductors.

In the course of my experimentations with such insulating materials I have discovered that they may be considerably improved by hydrogenating them. This may be accomplished by treating them with hydrogen under pressure of 30-1000 lbs. or more and preferably at 50-200 lbs. per square inch while maintained in the temperature range of 30 C.-l50 C. A comparison of a hydrogenated cable cloth, for example, with the corresponding cable cloth which has not been treated in the manner aforesaid reveals that the former has improved tensile strength, greater slip, is of a rubbery nature rather than tacky and pitchy, has greater dielectric'strength, improved power factor losses and greater life at 125 C. In addition, the thickness of the cable cloth after hydrogenation is increased as a result of said hydrogenation.

The coating and impregnating composition for a base for the production of cable cloth may be made by employing'one or more heat polymerizable unsaturated fatty oils of vegetable, animal or marine origin. Examples of such oils are linseed oil, castor oil, soya-bean oil, China-wood oil, oiticica oil, perilla oil, fish oils and the like as well as various fractions thereof. These various oils may be employed in their raw, refined and/or blown state. Mixed with said oil is a quantity of an oil soluble resinous material for imparting hardness to the film and to impart thereto desired electrical properties. The ratio by weight of said oil to said resinous material is in the range of 1-3 to 9-1 and preferably in the range of 2-3 to 8-1. The mixture is heated until solution takes place and the desired viscosity is attained. Examples of some of the resinous materials are oil-soluble phenol-aldehyde resins, terpene resins, alkyd resins, furfural-ketone resins, phenolic ether resins, asphalts, gilsonite, vegetable, animal and marine pitches and pitchy residues. Then to said solution is added a quantity of one or a combination of two or more metallie driers. These driers are oil soluble and in general are the metal salts of an organic compound, such as organic acids. Examples of the metals, are manganese, copper, lead, cobalt, iron, zinc, platinum, nickel, rhodium, etc. and examples of the organic acids are naphthenic, abietic, oleic, resinic acids, etc., as well as tall oil, etc. The ratio by Weight of the metal salt to the fatty oil is in the range of .1-100 to 1.5100. If desired there may also be added to said solution a quantity of any desirable silicone which may be l-30 parts by weight for each 100 parts of the combined weights of said oil and resinous material. A quantity of a thinner or diluent is then added to the mass to thin it to the desired consistency. There also may be added a quantity of a lubricant, such as a mineral hydrocarbon oil, measuring by weight 10-20 parts for each 100 parts of the thinned mass. The thinned product is then ready for coating a flexible base or cloth composed of cotton, glass or any other desirable material. The thickness of the base is in the range of 1-5.5 mils. The base is impregnated and coated with said thinned coating material, after which it is doctored to the required thickness and subjected to heat to drive off the thinner, which may be mineral spirits, etc., and to thermoset said coating to provide a cable cloth having an over-all thickness of 6-15 mils and a coating of 1.5-6 mils on either side of the base.

The cable cloths of the aforesaid type are improved in the manner heretofore set forth by treating them with hydrogen as before described.

The following is a specific example set forth merely by way of illustrating a particular method for producing a particular cable cloth and also illustrating the invention and to show comparative tests of the unhydrogenated and hydrogenated cable cloth:

100 pounds of dehydrated castor oil (Castung GI-I) pounds of an oil soluble phenol-aldehyde resin (Bakelite 2-54) and 113 pounds of blown petroleum pitch (Robertson 292) were heated together for 30 minutes at 580-600 F. Then an additional 287 pounds of dehydrated castor oil was added and the mass was maintained at 580-600 F. until the mass acquired a 2 cm. flow characteristic. Then to the mass was added 129 pounds of linseed oil (A. D. M. 75-5) to chill back to 400 F. Subsequently 292 pounds of mineral spirits and 2 pounds of naphenate metallic driers, containing 15.5 grams of manganese and 83.4 grams of lead, were added and agitated to provide a homogeneous mass. This mass was then filtered and using an edgewise coater, was applied to a cotton cloth (4.5 mils, count 64-60) to impregnate and coat the same. Three coats were applied with each maintained for 20 minutes at approximately 325 F. resulting in a cable cloth Whose overall thickness meassured 12.3 mils average and whose coating was thermoset. A sample of this normally finished product was cut in half, and only one half was wound with porous or open separators such asv coarsely woven glass, metallic or metallic coated mesh cloth between the individual turns and placed in a steel autoclave immersed in a hot water bath (l50-200 F.). Themetal chosen for said cloth is preferably a catalytic metal or any other material generally having good catalytic effect for hydrogenation in general. The autoclave containing the material to be hydro,- genated was evacuated and then flushed with hydrogen to strip out any residual or adhering oxygen. Then it was filled with hydrogen at a pressure of 50-60 pounds per square inch and maintained for 24 hours under these conditions of temperature and pressure. The thus hydrogenated cable cloth was removed from .the autoclave and subjected to various tests as was the unhydrogenated half of cable cloth so that the characteristics thereof before and after hydrogenation could be ascertained.

Before After Properties Hydro ,Hydrogenation gcnation Tensile (Warp) "rounds per inch widtln. 41. 43.9 Tear (Warp) grams 419 392 Elongation at 70 F. .per cent.. 1. 7 Film Hardness. 750 500 EA l, 160 1,200 12. 3 13. 0

y "per cent" 3. 65 3.61 24 hrs. 65% rel. hum. do 11.54 10. 62 168 hrs. 65% re] hum do 25. 78 16. 28 Life at 150 0... .hours 179 250 Life at 125 0.. .do 600 750 Slip value low high Surface character 1 Sticky, tacky and pitchy.

'- N on-tacky, rubbery and comparatively dry.

It is also within the spirit of this invention to dip, spray or otherwise coat an electrical unit, such as coils or other electrical conductors for motors, generators, etc. with a coating composition of the aforesaid nature and then subjecting the so-coated part to hydrogenation treatment as hereinbefore described to improve the characteristics of the insulator coating therefor.

Having thus described my invention, What I claim and desire to protect by Letters Patent is:

1. The method of treating a combination of a base carrying a thermoset composition produced by heat converting a composition comprising heat polymerizable unsaturated fatty oil, oil-soluble resinous material and oil-soluble metallic drier and whose maximum average thickness is mils, comprising maintaining said combination incontact with an atmosphere composed essentially of hydrogen under pressure of 30-1000 pounds per square inch and in the temperature range of 30 C.l50 C. until the life at 125 C. of said composition is materially greater than said characteristic of a corresponding untreated composition.

2. The method of treating a combination of a basecarrying a thermoset composition produced by heat converting a composition comprising heat polymerizable unsaturated fatty oil, oil-soluble resinous material, the ratio by weight of said oil to said resinous material being in the range 02243 to 9-1, and oil-soluble metallic drier and whose maximum average thickness is 15 mils, comprising maintaining said combination in contact with an atmosphere composed essentially of hydrogen under pressure of 30-1000 pounds per square inch and'in the temperature range of 30 C.-150 C. until the life at C. of said composition is materially greater than said characteristic of a corresponding untreated composition.

3. The method of treating a combination of a base carrying a thermoset composition produced b-y-heat converting a composition comprising heat polymerizable unsaturated fatty oil, oil-soluble resinous material and oil-soluble metallic drier and whose maximum average thickness is 15 mils, comprising disposing-said combination in layers with a hydrogen .admitting separator between the-layers and while so disposed, maintaining them in contact-with an atmosphere composed essentially of hydrogen under pressureof at least 30 pounds per square inch and at a temperature of 30 C.-l50 C. until the life at 125 C. of said composition is materially greater than said characteristic of a corresponding untreated composition.

4. A product produced according to claim 1.

5. The-method of treating a combination of a basecarrying a thermoset, tacky and pitchy composition produced by heat converting heat polymerizable unsaturated fatty oil, resinous mate rial soluble in said oiland metallic drier soluble in said oil, the ratio-by weight of said oil to said resinous materialbeingin the range of 1-3 to 9-1, the ratio by weight of said drier to said oil being'in-the range of .1-100 to 15-100, the maximum average thickness of said thermoset composition being 15 mils, comprising maintaining said combination in contact with an atmosphere composed essentially of hydrogen underpressure of 30-1000" pounds per squareinch and in the temperature range of 30 C.- C. until said thermoset composition is converted from thetacky and pitchy state to a-substantially nontacky, rubbery andcomparatively dry state.

MORTIMER, T. HARVEY.

REFERENCES CITED The" following references are of'record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,037,331 Kittredge et a1 Apr. 14, 1936 2,072,143 Ubben Mar. 2, 1937 2,121,580 Berliner et a1 June 21, 1938 

1. THE METHOD OF TREATING A COMBINATION OF A BASE CARRYING A THERMOSET COMPOSITION PRODUCED BY HEAT CONVERTING A COMPOSITION COMPRISING HEAT POLYMERIZABLE UNSATURATED FATTY OIL, OIL-SOLUBLE RESINOUS MATERIAL AND OIL-SOLUBLE METALLIC DRIER AND WHOSE MAXIMUM AVERAGE THICKNESS IS 15 MILS, COMPRISING MAINTAINING SAID COMBINATION IN CONTACT WITH AN ATMOSPHERE COMPOSED ESSENTIALLY OF HYDROGEN UNDER PRESSURE OF 30-1000 POUNDS PER SQUARE INCH AND IN THE TEMPERATURE RANGE OF 30* C.-150* C. UNTIL THE LIFE AT 125* C. OF SAID COMPOSITION IS MATERIALLY GREATER THAN SAID CHARACTERISTIC OF A CORRESPONDING UNTREATED COMPOSITION. 